EP3151328B1 - Rechargeable battery and separator used therein - Google Patents

Rechargeable battery and separator used therein Download PDF

Info

Publication number
EP3151328B1
EP3151328B1 EP15799912.9A EP15799912A EP3151328B1 EP 3151328 B1 EP3151328 B1 EP 3151328B1 EP 15799912 A EP15799912 A EP 15799912A EP 3151328 B1 EP3151328 B1 EP 3151328B1
Authority
EP
European Patent Office
Prior art keywords
dendrite
separator
react
layer
alkali metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP15799912.9A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP3151328A4 (en
EP3151328A1 (en
Inventor
Kotaro Kobayashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
WL Gore and Associates GK
Original Assignee
WL Gore and Associates GK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by WL Gore and Associates GK filed Critical WL Gore and Associates GK
Publication of EP3151328A1 publication Critical patent/EP3151328A1/en
Publication of EP3151328A4 publication Critical patent/EP3151328A4/en
Application granted granted Critical
Publication of EP3151328B1 publication Critical patent/EP3151328B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/574—Devices or arrangements for the interruption of current
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2200/00—Safety devices for primary or secondary batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a secondary battery and a separator used therein. More particularly, the present invention relates to a secondary battery that is able to inhibit the growth of a dendrite that can generate from an electrode comprising alkali metal and a separator used therein.
  • a chargeable and dischargeable secondary battery generally has a structure that prevents direct electrical contact between a positive electrode and a negative electrode by separating the positive electrode (cathode) and the negative electrode (anode) with a porous polymer membrane comprising an organic electrolyte solution.
  • V 2 O 5 , Cr 2 O 5 , MnO 2 , TiS 2 , and the like are known as a positive electrode active material of this nonaqueous electrolyte secondary battery.
  • LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , and the like are used as a 4-V class positive electrode active material.
  • alkali metals including metallic lithium have been studied so much. This is because, in particular, metallic lithium has a very high theoretical energy density (3861 mAh/g by weight capacity density) and a low charge/discharge potential (-3.045 V vs. SHE) and thus is considered to be an ideal negative electrode material.
  • an electrolyte solution for example, a lithium salt dissolved in a nonaqueous organic solvent is used, which salt has good ionic conductivity and negligible electrical conductivity.
  • a lithium salt dissolved in a nonaqueous organic solvent which salt has good ionic conductivity and negligible electrical conductivity.
  • Dendritic lithium lithium dendrite precipitates on the lithium surface of the negative electrode during charging.
  • the dendritic lithium grows as the charge and discharge is repeated, causing, for example, detachment from the lithium metal to thereby reduce cycle characteristics.
  • the dendritic lithium grows to the extent that it breaks through the separator, causing a short circuit of a battery, which can cause firing of the battery.
  • Patent Document 1 JP 05-258741 A proposes using a separator with a smaller pore size than that of conventional ones so that a crystal that grows from the negative electrode side does not grow at pore portions in order to inhibit the growth of such a dendritic crystal (dendrite).
  • WO 2013/084368 discloses a lithium secondary battery separator including a stack body of a base and a porous heat-resistant polyimide film which covers at least one surface of the base.
  • the porous heat-resistant polyimide film has holes which are regularly arrayed three-dimensionally and a film thickness of 5-20 ⁇ m. Penetration damage to the separator by growth of dendrite-shaped lithium is said to be avoided.
  • JP 3463081 discloses a separator with chemical resistance, heat resistance and hydrophilic properties which is free from wetting unevenness which provides improved electrochemical device characteristics, such as safety and reliability.
  • An electrochemical reacting device using such a separator is also disclosed.
  • the separator consists of a metal oxide composite polymer porous body in which at least the fine fiber node or pore wall surface of a polymer porous body, such as a fluorine resin porous body film, is covered with a metal oxide consisting of the dried body of a metal oxide water-containing gel formed by the gelating reaction of a hydrolytic metal-containing organic compound.
  • US 2003/049538 discloses an electrochemical energy storage device with at least two electrodes and an electrolyte, a carrier material for the electrolyte being disposed between the electrodes, and the carrier material including a porous material in whose inner pore structure a perfluoropolyether and/or fluorinated substance is present.
  • JP 2007/149507 discloses a nonaqueous electrolyte secondary battery in which a separator with a shut down function and a separator for maintaining electron insulating characteristics are provided.
  • the separator consists of at least two layers of which the separator with the shut down function and the high heat resistance separator are overlapped without mutual adhesion.
  • Patent Document 2 JP 09-293492 A proposes using an expanded porous polytetrafluoroethylene (PTFE) membrane as a battery separator with high porosity, mechanical strength, and heat resistance and treating the surface and internal pore surface of the expanded porous PTFE membrane to modify these surfaces to a hydrocarbon or carbon oxide compound and cover them.
  • PTFE polytetrafluoroethylene
  • the separator (PTFE) is in contact with the whole surface of a negative electrode (lithium), and consequently a reaction occurs at the electrode/separator interface, whereby the lithium electrode surface is covered with a reaction product, which adversely affects the electrolysis/precipitation of the lithium.
  • Patent Document 2 describes that the reaction between lithium and a PTFE substrate can be prevented by treating the surface and internal pore surface of the expanded porous PTFE membrane to modify these surfaces to a hydrocarbon or carbon oxide compound and cover them.
  • Patent Document 3 U.S. Patent No. 5,427,872 discloses a lithium electrode (anode) secondary battery comprising a first porous separator and a second separator, wherein the first separator is adjacent to the anode and formed by an aliphatic hydrocarbon resin that does not react with lithium and lithium ions, and the second separator is located between the first separator and the cathode and comprises thermoplastic polytetrafluoroethylene that reacts with lithium metal.
  • Patent Document 1 to Patent Document 3 described above are all for achieving a secondary battery using lithium metal.
  • Patent Document 1 cannot completely prevent the growth of a lithium dendrite in principle as long as ions pass therethrough to cause precipitation despite the small pores.
  • Patent Document 2 although the reaction between the electrode (lithium)/the separator (fluorine content) can be prevented, the growth of a lithium dendrite cannot be prevented.
  • the heating value (theoretical value) of the reaction of a lithium dendrite and polytetrafluoroethylene described in Patent Document 3 is not sufficient to dissolve polytetrafluoroethylene and form non-porous blocks. Actually, retests were carried out, but polytetrafluoroethylene could not be dissolved to form non-porous blocks by this reaction.
  • Patent Document 1 to Patent Document 3 a hydrophilizing treatment of the separator is neither disclosed nor suggested. Therefore, it can be thought that a hydrophilizing treatment has not been performed in Patent Document 1 to Patent Document 3.
  • An unhydrophilized separator does not provide sufficient battery performance because it does not get wet sufficiently by an electrolyte solution and ions cannot move smoothly.
  • Patent Document 3 PTFE is dissolved by heat of reaction between PTFE and lithium to form blocks
  • a hydrophilizing treatment has not been carried out in the invention of Patent Document 3, and therefore sufficient battery performance cannot be obtained.
  • Patent Document 2 is also on the assumption that PTFE reacts with lithium, and if hydrophilization is complete, the problem of Patent Document 2 does not exist in the first place. In other words, it is considered that a hydrophilizing treatment has not been carried out also in the invention of Patent Document 2, and therefore sufficient battery performance cannot be obtained.
  • Patent Document 1 can not completely prevent the growth of a lithium dendrite in principle. Therefore, if a hydrophilizing treatment is carried out to make PTFE unreactive with lithium, the growth of a dendrite is rather promoted, and it is more likely that the dendrite reaches the cathode to cause a short circuit.
  • alkali metals other than lithium also have a very high theoretical energy density and a low charge/discharge potential and can generate a dendrite.
  • an object of the present invention is to provide a secondary battery that is certainly able to inhibit the growth of a dendrite that can generate from an electrode comprising alkali metal and a separator used therein.
  • the present invention relates to a separator for a secondary battery according to appended claim 1 and a secondary battery comprising such a separator according to any one of appended claims 2 to 15.
  • the present invention thus provides the following aspects.
  • the present invention provides a secondary battery that is certainly able to inhibit the growth of a dendrite that can generate from an electrode comprising alkali metal and a separator used therein.
  • Secondary batteries are basically composed of a positive electrode/negative electrode and a separator comprising an electrolyte that acts as an ion-conducting medium between the two electrodes.
  • the negative electrode comprises alkali metal.
  • Alkali metals have a very high theoretical energy density and a low charge/discharge potential and thus are considered to be an ideal negative electrode material.
  • lithium has a very high theoretical energy density (3861 mAh/g by weight capacity density) and a low charge/discharge potential (-3.045 V vs. SHE) and thus is considered to be an ideal negative electrode material.
  • ions in the separator move from the positive electrode to the negative electrode.
  • the ions move in the reverse direction back to the positive electrode.
  • dendritic alkali metal precipitates on the surface of the negative electrode comprising alkali metal.
  • the dendrite grows as the charge and discharge is repeated, causing, for example, detachment from the negative electrode metal to thereby reduce cycle characteristics. In the worst case, the dendrite grows to the extent that it breaks through the separator, causing a short circuit of a battery, which can cause firing of the battery.
  • the separator serves to prevent a short circuit by separating the positive electrode and the negative electrode and to ensure high ionic conductivity by retaining an electrolyte necessary for cell reaction.
  • the separator comprises a layer of tetrafluoroethylene (TFE) polymer or copolymer. This is because the tetrafluoroethylene (TFE) polymer or copolymer has high porosity, high strength, and excellent heat resistance. This tetrafluoroethylene (TFE) polymer or copolymer contains fluorine.
  • TFE tetrafluoroethylene
  • the present inventor arrived at the idea of taking advantage of the characteristics of this fluorine to react with alkali metal. Namely, the present invention has been completed based on a novel idea of the present inventor that the growth of a dendrite can be inhibited by reacting fluorine with the dendrite of alkali metal.
  • the tetrafluoroethylene (TFE) polymer or copolymer constituting the separator is fluororesin and hydrophobic in itself.
  • the separator must be those in which ions existing in an electrolyte solution (aqueous solution, organic solvent, and the like) are able to pass through a porous body or fibers of the separator and move from one place to the other place separated by the separator.
  • the tetrafluoroethylene (TFE) polymer or copolymer constituting the separator is subjected to a hydrophilizing treatment.
  • the hydrophilizing treatment must be carried out sufficiently such that the separator has hydrophilicity and that the interior of the separator is made wet with an electrolyte solution.
  • carrying out the hydrophilizing treatment at a rate of not less than 10% and not more than 80% is one of the characteristics.
  • at least a part of the separator shall not be hydrophilized, whereby the fluorine content that is contained in tetrafluoroethylene (TFE) constituting the separator and reacts with a dendrite will remain exposed.
  • TFE tetrafluoroethylene
  • this fluorine content certainly reacts with a dendrite to inhibit the growth of the dendrite.
  • the rate of the hydrophilizing treatment is less than 10%, the hydrophilicity is not sufficient, i.e., the ionic conductivity is not sufficient.
  • a battery will have a high internal resistance, and the original battery performance cannot be obtained.
  • the rate of the hydrophilizing treatment is more than 80%, the fluorine content that reacts with an alkali metal dendrite is not sufficiently exposed, and the dendrite growth-inhibiting effect decreases.
  • the method of hydrophilizing treatment is not particularly limited, and the method described in Japanese Patent No. 3463081 , which is patented by the present applicant, may be used.
  • the method in summary, is a method in which a gelled product in the form of a solution formed by partial gelation reaction of a hydrolyzable metal-containing organic compound (for example, silicone alkoxide such as tetraethoxysilane) is attached to at least the microfibrils/micronodes or pore wall surface of a polymeric porous body having continuous pores to complete the gelation, thereby providing a structure of being covered with a metal oxide gel formed as a result of drying.
  • a hydrolyzable metal-containing organic compound for example, silicone alkoxide such as tetraethoxysilane
  • hydrophilization can be achieved by covering with silica gel.
  • hydrophilic polymer for example, PVA or the like
  • a hydrophilic polymer may be impregnated into a porous body, and then dried for formation to provide a structure of being covered with the hydrophilic polymer.
  • the state of hydrophilization can be measured by a surface analysis method, and, for example, tetrafluoroethylene (TFE) that has been subjected to a hydrophilizing treatment is measured using a Field Emission-Scanning Electron Microscope (FE-SEM for short).
  • TFE tetrafluoroethylene
  • FE-SEM Field Emission-Scanning Electron Microscope
  • the state of a porous structure is confirmed on an electron micrograph.
  • the state of TFE having a hydrophilized layer of several nm to several tens of nm on its surface of nodes and fibrils while maintaining the porous structure can be confirmed.
  • the ratio of elements present on a sample surface is measured using a composition analysis function of the electron microscope.
  • SiOx is used as a hydrophilizing treatment material to cover TFE, Si and O are present on the sample surface.
  • the rate of hydrophilization is determined from the ratio of F present on the surface after hydrophilizing treatment.
  • the secondary battery of the present invention comprises a layer that does not react with a dendrite of the alkali metal between the negative electrode comprising alkali metal and the separator comprising a layer of tetrafluoroethylene (TFE) polymer or copolymer that reacts with a dendrite of the alkali metal.
  • TFE tetrafluoroethylene
  • the fluorine content in the separator (comprising the layer of tetrafluoroethylene (TFE) polymer or copolymer) reacts with the alkali metal of the negative electrode on the whole contacting surface, and defluoridation of the separator proceeds with or without the occurrence of a dendrite; as a result, high porosity, high strength, and heat resistance cannot be maintained. Namely, the function as a separator cannot be performed.
  • the layer that does not react with a dendrite as well as the separator serves to prevent a short circuit by separating the positive electrode and the negative electrode and to ensure high ionic conductivity by retaining an electrolyte necessary for cell reaction.
  • a material having high porosity, high strength, and excellent heat resistance is used. Therefore, a dendrite that starts to grow from the negative electrode grows through a hole in the layer that does not react with a dendrite. Since the layer that does not react with a dendrite does not react with a dendrite, its hole structure is soundly maintained even when a dendrite has grown. A dendrite passes through the hole in the layer that does not react with a dendrite and finally reaches the separator.
  • the separator comprises a layer of tetrafluoroethylene (TFE) polymer or copolymer
  • TFE tetrafluoroethylene
  • the fluorine content contained in the separator reacts with a dendrite of the alkali metal, and the growth of a dendrite stops here.
  • the time when and the place where a dendrite reaches the separator vary depending on the path of the hole in the layer that does not react with a dendrite, and reaction between a dendrite and the fluorine content in the separator occurs dispersedly in terms of time and place.
  • A means alkali metal.
  • layer that does not react with a dendrite means that the layer substantially does not react with a dendrite, i.e., does not substantially undergo defluoridation.
  • “Not substantially undergo defluoridation” means that defluoridation does not proceed to the extent that the structure of the layer cannot be maintained.
  • the layer that does not react with a dendrite in the present invention may contain a fluorine-containing substance such as pVDF. Fluorine contained in pVDF can slightly react with alkali metal of a dendrite, but defluoridation cannot proceed to the extent that the structure of the layer that does not react with the dendrite cannot be maintained.
  • layer that does not react with a dendrite in the present invention should not be interpreted restrictively to mean that fluorine does not react with a dendrite at all. Needless to say, when the layer that does not react with a dendrite does not contain fluorine, reaction with a dendrite naturally cannot occur.
  • the standard deviation of opening areas of pores on the negative electrode side surface of the layer that does not react with a dendrite is 0.1 ⁇ m 2 or less.
  • the standard deviation of opening areas of pores is 0.1 ⁇ m 2 or less, whereby the possibility of a short circuit can be significantly reduced.
  • the standard deviation of opening areas of pores is determined as described below. First, the negative electrode side surface of the layer that does not react with a dendrite is photographed with an electron microscope; the opening area of each pore is measured from an image obtained; and its standard deviation is calculated.
  • pores having an opening area of less than 0.2 ⁇ m 2 are 75% or more based on the total number of the pores.
  • pores having an opening area of less than 0.2 ⁇ m 2 account for 75% or more of the total pores, it means that fine-textured pores are fully provided. If pores having an opening area of 0.2 ⁇ m 2 or more exist in an amount of more than 25% of the total pores, the pores having a relatively large opening increases the possibility that the growth of dendrites proceeds locally and temporarily, increasing the risk of occurrence of a short circuit.
  • the opening areas of pores are determined from an image of the negative electrode side surface of the layer that does not react with a dendrite taken with an electron microscope. Thus, the opening area of each pore and the number of pores obtained are compiled, and the ratio of the number of pores in a given range of opening areas to the total number of pores are determined.
  • the layer that does not react with a dendrite of the alkali metal may be hydrophilized.
  • the hydrophilization can provide the characteristic of not reacting with a dendrite of the alkali metal or improve the characteristic. This is probably because a hydrophilic group or hydrophilic substance is attached to the inner surface of pores of the layer that does not react with a dendrite and this hydrophilic group or hydrophilic substance does not react with a dendrite.
  • the hydrophilizing treatment applied to the separator mentioned above may be applied to the layer that does not react with a dendrite. Even if the layer that does not react with a dendrite is a part of the separator and contains the fluorine content that reacts with a dendrite, the fluorine content that reacts with a dendrite can be covered with a hydrophilic group or hydrophilic substance by progressing the hydrophilizing treatment of the inner surface of its pores, so that a reaction with a dendrite will not occur there. In other words, the hydrophilizing treatment can provide a layer that does not react with a dendrite.
  • any conventional material known or well-known as a positive electrode for a lithium secondary battery can be used.
  • metal chalcogenides which are able to occlude and release alkali metal ions such as sodium ions and lithium ions during charging and discharging, and the like are preferred.
  • metal chalcogenides include oxides of vanadium, sulfides of vanadium, oxides of molybdenum, sulfides of molybdenum, oxides of manganese, oxides of chromium, oxides of titanium, sulfides of titanium, and complex oxides and complex sulfides thereof.
  • Examples of such compounds include Cr 3 O 8 , V 2 O 5 , V 5 O 18 , VO 2 , Cr 2 O 5 , MnO 2 , TiO 2 , MoV 2 O 8 , TiS 2 V 2 S 5 MoS 2 , MoS 3 VS 2 , Cr 0.25 V 0.75 S 2 , Cr 0.5 V 0.5 S 2 , and the like.
  • LiMY 2 (M is a transition metal such as Co and Ni, and Y is a chalcogenide such as O and S), LiM 2 Y 4 (M is Mn, and Y is O), oxides such as WO 3 , sulfides such as CuS, Fe 0.25 V 0.75 S 2 , and Na 0.1 CrS 2 , phosphorus-sulfur compounds such as NiPS 8 and FePS 8 , selenium compounds such as VSe 2 and NbSe 3 , iron compounds such as iron oxides, and the like can also be used. Further, manganese oxides and lithium/manganese complex oxide having a spinel structure are also preferred.
  • the material include LiCoO 2 , LiCo 1-x Al x O 2 , LiCo 1-x Mg x O 2 , LiCo 1-x Zr x O 2 , LiMn 2 O 4 , Li 1-x Mn 2-x O 4 , LiCr x Mn 2-x O 4 , LiFe x Mn 2-x O 4 , LiCO x Mn 2-x O 4 , LiCu x Mn 2-x O 4 , LiAl x Mn 2-x O 4 , LiNiO 2 , LiNi x Mn 2-x O 4 , Li 6 FeO 4 , NaNi 1-x Fe x O 2 , NaNi 1-x Ti x O 2 , FeMoO 4 Cl, LiFe 5 O 8 , FePS 3 , FeOCl, FeS 2 , Fe 2 O 3 , Fe 3 O 4 , ⁇ -FeOOH, ⁇ -FeOOH, ⁇ -Li
  • an electrolyte solution is retained.
  • an alkali metal salt such as a sodium salt or a lithium salt dissolved in a nonaqueous organic solvent is used.
  • the electrolyte solution is not particularly limited as long as it has good ionic conductivity and negligible electrical conductivity, and any conventional material known or well-known as an electrolyte solution for a lithium secondary battery can be used.
  • nonaqueous solvents examples include acetonitrile (AN), ⁇ -butyrolactone (BL), ⁇ -valerolactone (VL), ⁇ -octanoic lactone (OL), diethyl ether (DEE), 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), dimethyl sulfoxide (DMSO), 1,3-dioxolane (DOL), ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl formate (MF), tetrahydrofuran (THF), 2-methyltetrahydrofuran (MTHF), 3-methyl-1,3-oxaziridin-2-one (MOX), sulfolane (S), and the like, which can be used alone or as a mixture of two
  • the alkali metal salt particularly, the lithium salt used for the electrolyte solution of the secondary battery
  • lithium salts such as LiPF 6 , LiAsF 6 , LiClO 4 , LiBF 4 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, and LiC 4 F 9 SO 3 , and one, or two or more of them are dissolved in the nonaqueous solvent described above at a concentration of about 0.5 to 2.0 M to obtain a nonaqueous electrolyte solution.
  • the layer that does not react with a dendrite of the alkali metal may be a part of the separator, and, in the layer that does not react with a dendrite of the alkali metal, the inner surface of its pores may be at least partially covered with a material that does not react with a dendrite.
  • the inner surface of its pores is at least partially covered with a material that does not react with a dendrite, and this part is defined as a layer that does not react with a dendrite of the alkali metal.
  • the separator comprises a layer of tetrafluoroethylene (TFE) polymer or copolymer, and the fluorine content contained in this layer reacts with a dendrite.
  • the layer of tetrafluoroethylene (TFE) polymer or copolymer, i.e., the fluorine content contained in this layer is covered with a material that does not react with a dendrite, a reaction between the fluorine content and a dendrite does not occur in this area, and this area can be a layer that does not react with a dendrite of the alkali metal.
  • TFE tetrafluoroethylene
  • a part of the separator is only at least partially covered with a material that does not react with a dendrite, the number of parts of the battery is reduced, which is advantageous in assembling a secondary battery.
  • the layer that does not react with a dendrite of the alkali metal may be independent of the separator.
  • the above-mentioned step of covering a part of the separator with a material that does not react with a dendrite is not necessary.
  • the layer that is independent of the separator and does not react with a dendrite of the alkali metal may comprise any one of glass comprising SiO x (0 ⁇ ⁇ ⁇ 2), polyvinylidene fluoride (PVDF), polyimide (PI), polyethylene (PE), or polypropylene (PP) or a mixture thereof. These materials do not cause a reaction with a dendrite of the alkali metal. In addition, these materials allow appropriate preparation of one having high porosity, high strength, and heat resistance. Although polyvinylidene fluoride (PVDF) contains fluorine content, a reaction between the fluorine content and a dendrite of the alkali metal will not occur to progress defluoridation, i.e., carbonization.
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • the layer that is independent of the separator and does not react with a dendrite of the alkali metal may comprise any one of inorganic oxides selected from the group consisting of alumina, titanium oxide, sodium oxide, calcium oxide, boron oxide, potassium oxide, and lead oxide or a mixture thereof and a binder. These materials also do not cause a reaction with a dendrite of the alkali metal. In addition, these materials also allow appropriate preparation of one having high porosity, high strength, and heat resistance.
  • the inner surface of its pores may be covered with a material other than tetrafluoroethylene (TFE) polymer or copolymer.
  • TFE tetrafluoroethylene
  • TFE tetrafluoroethylene
  • Materials other than tetrafluoroethylene (TFE) are less likely to react with a dendrite and able to further enhance the function of not reacting with a dendrite in the layer that does not react with a dendrite has.
  • the method of covering a material is not particularly limited, and a conventional method can be appropriately used depending on the material.
  • a material to be applied may be brought into solution for impregnation.
  • any method may be used such as vacuum pressure impregnation, vacuum impregnation, spraying, evaporation to dryness, metering bar method, die coating method, gravure method, reverse roll method, doctor blade method, knife coating method, and bar coating method.
  • the application method is not particularly limited, and, for example, any method such as metering bar method, die coating method, gravure method, reverse roll method, and doctor blade method may be used.
  • chemical modification and physical modification may be used.
  • the chemical modification include the method of adding a functional group to the inner surface of pores by acetylation, isocyanation, acetalization, or the like, the method of covering the inner surface of pores with organic matter or inorganic matter by chemical reaction, and the like.
  • the physical modification include, physical vapor deposition such as vacuum deposition, ion plating, and sputtering, chemical vapor deposition, plating methods such as electroless plating and electrolytic plating, and the like. These methods for covering may be used alone, or two or more thereof may be used in combination.
  • the layer that does not react with a dendrite is a part of the separator, to enhance the binding force between a material to be applied and a material to be covered (the raw material is tetrafluoroethylene (TFE)), if the inner surface of pores of the material to be covered (corresponding to the layer that does not react with a dendrite in a secondary battery) is subjected to a chemical treatment (alcohol substitution treatment, alkali treatment, or the like) or a physical treatment (corona treatment, plasma treatment, UV treatment, or the like) as a pretreatment to attach a surface functional group to an F-C bond at the inner surface of pores of the material to be covered, the adhesive strength will be enhanced.
  • a chemical treatment alcohol substitution treatment, alkali treatment, or the like
  • a physical treatment corona treatment, plasma treatment, UV treatment, or the like
  • the material other than tetrafluoroethylene (TFE) polymer or copolymer applied to the inner surface of pores of the layer that does not react with a dendrite may be any one of glass comprising SiO x (0 ⁇ x ⁇ 2), polyvinylidene fluoride (PVDF), polyimide (PI), polyethylene (PE), or polypropylene (PP) or a mixture thereof. These materials do not cause a reaction with a dendrite of the alkali metal. In addition, these materials allow appropriate preparation of one having high strength and heat resistance. Further, these materials can be applied to the inner surface of pores of the layer that does not react with a dendrite as appropriate (without blocking the pores) and are also able to maintain the high porosity of the layer that does not react with a dendrite as appropriate.
  • PVDF polyvinylidene fluoride
  • PI polyimide
  • PE polyethylene
  • PP polypropylene
  • SiO X (0 ⁇ x ⁇ 2) may be applied by Sol-Gel method.
  • Sol-Gel method starting from molecules having a hydrolyzable group, condensation is carried out to form particles dissolved in the form of colloidal dispersion (sol).
  • the sol generally can be used as a liquid coating material by not completing the condensation reaction.
  • a structure (gel) is formed by condensation after applied, and is built up to desired level in the pores. In this condensation, any other cross-linking mechanism (e.g., polymerization of organic functional groups) may optionally be used.
  • the gel is heat-treated or vacuum-treated to thereby remove the solvent remaining inside, further promoting densification. In this way, SiO x (0 ⁇ x ⁇ 2) can be applied to the internal surface of the pores.
  • the Sol-Gel method allows for easy production at a low temperature as compared to other methods (e.g., molten glass method, powder sintering method). Further, by utilizing chemical reaction, organic matter and inorganic matter can be composited since the production at a low temperature is possible.
  • TFE tetrafluoroethylene
  • TFE tetrafluoroethylene
  • TFE tetrafluoroethylene
  • An expanded porous membrane of tetrafluoroethylene (TFE) polymer or copolymer is suitably obtained by expanding a precursor formed by melt fusion of fine powders of tetrafluoroethylene (TFE) polymer or copolymer (see each description of JP 56-45773 B , JP 56-17216 B , and U.S. Patent No. 4187390 ).
  • tetrafluoroethylene (TFE) polymer or copolymer By controlling the fusion conditions of fine powders of tetrafluoroethylene (TFE) polymer or copolymer or the expanding conditions of a precursor, a membrane with high porosity and high strength can be produced.
  • tetrafluoroethylene (TFE) polymer or copolymer has a high melting point and is advantageous in that it does not melt even at 250°C or higher.
  • an expanded porous membrane of tetrafluoroethylene (TFE) polymer or copolymer is obtained in such a manner that a paste-like formed body obtained by mixing fine powders of tetrafluoroethylene (TFE) polymer or copolymer with a forming assistant is expanded after removing or without removing the forming assistant therefrom and optionally baked.
  • TFE tetrafluoroethylene
  • fibrils are oriented in the expanding direction, and, at the same time, a fibrous structure having holes between the fibrils is provided.
  • biaxial expanding fibrils spread radially, and a web-like fibrous structure is provided in which a number of holes defined by nodes and fibrils are present.
  • the porosity can be controlled by expanding as appropriate.
  • the porosity is not particularly restricted as long as the electrolyte solution can be retained in the battery, and it may be preferably 30% or more, more preferably 60% or more, and still more preferably 80% or more in order to ensure impregnating ability and permeability.
  • the thickness of the porous membrane is not particularly restricted and may be determined as appropriate depending on the application. In the case of those which are arranged between the electrodes, it may be preferably from 1 ⁇ m to 1000 ⁇ m. When the thickness is less than 1 ⁇ m, handling can be difficult because of insufficient strength, and, on the other hand, when it is more than 1000 ⁇ m, it can be difficult to uniformly impregnate the electrolyte solution.
  • the thickness of the porous membrane arranged between the electrodes is more preferably from 10 ⁇ m to 500 ⁇ m and still more preferably from 20 ⁇ m to 200 ⁇ m.
  • This tetrafluoroethylene (TFE) polymer or copolymer is not particularly limited as long as it has high porosity, high strength, and heat resistance and can react with a dendrite of the alkali metal. More specifically, the tetrafluoroethylene (TFE) polymer or copolymer may be expanded polytetrafluoroethylene, perfluoro alkoxy alkane (PFA), tetrafluoroethylene/hexafluoropropene copolymer (FEP), ethylene/tetrafluoroethylene copolymer (ETFE), or ethylene/chlorotrifluoroethylene copolymer (ECTFE) or a mixture thereof.
  • PFA perfluoro alkoxy alkane
  • FEP tetrafluoroethylene/hexafluoropropene copolymer
  • ETFE ethylene/tetrafluoroethylene copolymer
  • ECTFE ethylene/chlorotrifluoroethylene copolymer
  • the thickness of the layer that does not react with a dendrite of the alkali metal may be 0.1 ⁇ m or more.
  • a dendrite starts to grow from the negative electrode, passes through the hole in the layer that does not react with a dendrite, and finally reaches the separator.
  • the separator To disperse the time when and the place where a dendrite reaches the separator so that the fluorine content in the separator will not temporally and locally react with a dendrite to cause defluoridation, i.e., carbonization, it is preferable to adjust the layer that does not react with a dendrite of the alkali metal to have an appropriate thickness. When the thickness is as described above, the time when and the place where a dendrite reaches the separator will be sufficiently dispersed.
  • the thickness of the layer may be preferably not less than 1.0 ⁇ m and more preferably not less than 10 ⁇ m. There is no particular upper limit on the thickness of the layer, and the thickness can be set as appropriate from the standpoint of reducing the space for the secondary battery.
  • the separator may at least comprise fluorine that can react with the total mass of the alkali metal constituting the negative electrode.
  • the reaction of the alkali metal constituting the negative electrode will complete in the separator because the separator comprises fluorine that can react with the total mass of the alkali metal constituting the negative electrode. Therefore, a short circuit from the negative electrode to the positive electrode due to penetration of a dendrite through the separator can be certainly prevented.
  • the alkali metal constituting the negative electrode may be lithium or sodium.
  • metallic lithium has a very high theoretical energy density (3861 mAh/g by weight capacity density) and a low charge/discharge potential (-3.045 V vs. SHE) and thus is considered to be an ideal negative electrode material.
  • Metallic sodium also has a high theoretical energy density and a low charge/discharge potential. Although lithium or sodium has been reported to grow as a dendrite, the present invention can inhibit such growth of a dendrite.
  • the secondary battery according to the present invention may further include a shutdown layer.
  • the shutdown layer is a layer having a shutdown function.
  • the shutdown function is a function of blocking a current when the temperature of the battery is elevated, i.e., a function of arresting thermal runaway of the battery.
  • the shutdown layer may be, but is not limited to, a layer having micropores, the melting point of which is relatively low such that the micropores are blocked when the temperature of the battery is elevated to a certain temperature or higher.
  • a polyolefin, in particular, polyethylene microporous membrane may be used as the shutdown layer.
  • the shutdown layer may be not only a membrane but also nanofiber web, fiber web, or the like.
  • the shutdown layer may be those which include heat-reactive microspheres or a PTC element.
  • the shutdown layer may be located between the separator and the positive electrode.
  • the shutdown layer Since the shutdown layer is intended to block a current, it may be located anywhere between the positive electrode and the negative electrode in the secondary battery, and the shutdown layer may be located between the separator and the positive electrode. In this case, even if by any chance a dendrite should continue to grow, penetrate the separator, and reach the shutdown layer, heat generation due to defluoridation reaction between the dendrite (alkali metal) and the separator (TFE) will cause the shutdown layer to melt to achieve blocking. Thus, a short circuit between the negative electrode and the positive electrode due to penetration of a dendrite through the separator can be certainly prevented.
  • the present invention also relates to a separator used in the secondary battery described above.
  • a PTFE membrane (available from W. L. Gore & Associates, Inc.) was employed in Examples 1 to 9 and Comparative Example 4.
  • Comparative Example 1 to Comparative Example 3 generally available porous membranes shown in Table 1 were employed.
  • the membrane thickness, except for a glass fiber cloth was about 25 ⁇ m, and the porosity was near about 50%.
  • the membrane thickness of the glass fiber cloth was 100 ⁇ m.
  • silica was used to hydrophilize the separator.
  • the rate of hydrophilization was varied between 10% and 80% (20% to 90% in terms of internal exposed rate).
  • One hundred parts of tetraethoxysilane (available from Shin-Etsu Silicone), 52 parts of water, and 133 parts of ethanol were allowed to react at 80°C for 24 hours under reflux where the moisture from the outside air is blocked using a calcium chloride tube to prepare a partially gelled solution of metal oxide precursor.
  • the PTFE membrane described above was impregnated with a diluent of this solution, and then immersed in warm water at 60°C to complete the gelation.
  • Example 1 as a layer that does not react with a dendrite, the covering material or laminated material shown in Table 1 was provided between the separator and the negative electrode.
  • the separator was coated with SiOx (glassy substance) as a layer that does not react with a dendrite.
  • SiOx coating agent (New Technology Creating Institute Co., Ltd., SIRAGUSITAL B4373 (A), solid content: 60%) was dissolved in an IPA solvent to adjust the solid content concentration of the SiOx coating agent to 5% .
  • a porous PTFE film having a thickness of 25 ⁇ m was coated only on the surface layer with the SiOx coating agent subjected to the concentration adjustment described above by the gravure coating method.
  • the thickness of the layer that does not react with a dendrite was 0.2 ⁇ m. The thickness was determined by observing the thickness of the SiOx layer on the PTFE membrane (separator) surface using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • Example 6 PVDF (maker: ARKEMA, specification: KYNAR710) was dissolved in a given organic solvent to a given concentration, and the resultant was applied and dried in the same manner as in Example 1.
  • Example 7 PI (maker: Hitachi Chemical Co., Ltd., specification: HCI) dissolved in a given organic solvent was applied, dried, and cured in the same manner as in Example 1.
  • Example 8 as a layer that does not react with a dendrite, a PE porous membrane (membrane thickness: 25 ⁇ m, porosity: 50%) was laminated on the separator.
  • Example 9 as a layer that does not react with a dendrite, a PP porous membrane (membrane thickness: 25 ⁇ m, porosity: 50%) was laminated on the separator.
  • Example 1 As shown in Table 1, 50% of the inner surface of pores was covered with silica, and the internal exposed rate was 50%.
  • X-ray Photoelectron Spectrometer JPS-9200S for microanalysis manufactured by JEOL Ltd. was used. The measurement conditions were as follows: filament current: 4.5A; and accelerating voltage: 4.0 eV.
  • This apparatus was used to quantitatively determine the amount of F, O, C, and Si on the pore inner surface.
  • F/C 2:1 (66.7:33.3%). Based on this ratio, the coverage of silica was calculated from the ratio of the surface F quantitated.
  • This coin cell was used to perform a charge-discharge test (coin cell cycle by Li/Li).
  • the charge and discharge measurement was carried out using a battery charge and discharge apparatus (HJ1001SM8A) manufactured by HOKUTO DENKO CORP.
  • a charge-discharge test at a current density of 10 mA/cm 2 for 30 minutes (DOD: depth of discharge, about 25%) was repeated. The number of cycles until an internal short-circuit occurs due to a dendrite was calculated. The results are shown in Table 2.
  • the secondary battery of the present invention is able to inhibit the growth of a dendrite that can generate from an electrode comprising alkali metal.
  • a coin cell was produced in the same manner as in Example 1, and the charge-discharge test was repeated until an internal short-circuit occurs.
  • the opening areas of pores on the negative electrode side surface of the layer that does not react with a dendrite were as shown in Table 3.
  • Table 3 Properties of opening area and the number of cycles before short circuit Sample Standard deviation Ratio of pores having opening area less than 0.2 ⁇ m 2 Number of cycles before short circuit A 0.01 100 1400 B 0.02 95 1200 C 0.05 80 500 D 0.1 70 300 E 0.1 50 200 F 0.25 50 120 G 0.25 70 180 H 0.5 40 100 I 0.6 50 60 J 1 30 20
  • FIG. 2 is a graph showing the relationship between the standard deviation of opening areas and the number of cycles before a short circuit.
  • the standard deviation of opening areas decreased, the number of cycles before a short circuit increased.
  • the rate of increase of the number of cycles before a short circuit started to rise.
  • the standard deviation of opening areas falls below about 0.1 ⁇ m 2
  • the number of cycles before a short circuit significantly increased.
  • the standard deviation decreased to 0.05 ⁇ m 2 or less, 0.02 ⁇ m 2 or less, and 0.01 ⁇ m 2 or less, the number of cycles before a short circuit steeply increased.
  • FIG. 3 is a graph showing the relationship between the ratio of pores having an opening area of less than 0.2 ⁇ m 2 and the number of cycles before a short circuit.
  • the ratio of such pores increased, the number of cycles before a short circuit increased.
  • the ratio of such pores is about 40%, the rate of increase of the number of cycles before a short circuit started to rise.
  • the ratio of such pores exceeds about 70%, the number of cycles before a short circuit significantly increased.
  • the ratio of pores increased to 80% or more, 95% or more, and 100%, the number of cycles before a short circuit steeply increased.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)
  • Battery Electrode And Active Subsutance (AREA)
EP15799912.9A 2014-05-26 2015-05-26 Rechargeable battery and separator used therein Active EP3151328B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014108233 2014-05-26
PCT/JP2015/065120 WO2015182615A1 (ja) 2014-05-26 2015-05-26 二次電池およびそれに用いるセパレータ

Publications (3)

Publication Number Publication Date
EP3151328A1 EP3151328A1 (en) 2017-04-05
EP3151328A4 EP3151328A4 (en) 2017-11-15
EP3151328B1 true EP3151328B1 (en) 2022-03-23

Family

ID=54698940

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15799912.9A Active EP3151328B1 (en) 2014-05-26 2015-05-26 Rechargeable battery and separator used therein

Country Status (7)

Country Link
US (1) US10181593B2 (zh)
EP (1) EP3151328B1 (zh)
JP (1) JP6297145B2 (zh)
KR (1) KR101950083B1 (zh)
CN (1) CN106415913B (zh)
CA (1) CA2950400C (zh)
WO (1) WO2015182615A1 (zh)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6982398B2 (en) 2004-06-01 2006-01-03 Illinois Tool Works Inc. Fuel saving engine driven welding-type device and method of use
JP6472822B2 (ja) 2017-03-03 2019-02-20 住友化学株式会社 非水電解液二次電池用セパレータ
KR102201347B1 (ko) * 2017-06-15 2021-01-08 주식회사 엘지화학 배터리 모듈과 이를 포함하는 배터리 팩 및 자동차
WO2019241291A1 (en) * 2018-06-11 2019-12-19 William Marsh Rice University Systems and methods of detecting li dendrites
FR3084528B1 (fr) * 2018-07-27 2022-11-18 Arkema France Anode pour batterie li-ion
JP7172486B2 (ja) * 2018-11-15 2022-11-16 トヨタ自動車株式会社 全固体リチウム二次電池、及び全固体リチウム二次電池の劣化判定方法
JP6881541B2 (ja) * 2019-10-09 2021-06-02 ダイキン工業株式会社 含フッ素ポリマーを含有する組成物および架橋物

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3962153A (en) 1970-05-21 1976-06-08 W. L. Gore & Associates, Inc. Very highly stretched polytetrafluoroethylene and process therefor
CA962021A (en) 1970-05-21 1975-02-04 Robert W. Gore Porous products and process therefor
JPH05258741A (ja) 1992-03-11 1993-10-08 Matsushita Electric Ind Co Ltd 非水電解質二次電池用セパレータ
JP2943127B2 (ja) 1992-11-30 1999-08-30 キヤノン株式会社 二次電池
US5427872A (en) * 1993-11-17 1995-06-27 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Dendrite preventing separator for secondary lithium batteries
JP3463081B2 (ja) 1995-03-15 2003-11-05 ジャパンゴアテックス株式会社 電気化学反応装置用セパレータ及びそれを用いた電気化学反応装置
JPH09293492A (ja) 1996-04-25 1997-11-11 Nippon Telegr & Teleph Corp <Ntt> 電池用セパレータ
US20030049538A1 (en) * 2001-08-02 2003-03-13 Wolfgang Buerger Electrochemical energy storage device
US9368775B2 (en) * 2004-02-06 2016-06-14 Polyplus Battery Company Protected lithium electrodes having porous ceramic separators, including an integrated structure of porous and dense Li ion conducting garnet solid electrolyte layers
JP4986009B2 (ja) * 2005-04-04 2012-07-25 ソニー株式会社 二次電池
JP2007149507A (ja) * 2005-11-28 2007-06-14 Sanyo Electric Co Ltd 非水電解質二次電池
JP4801706B2 (ja) 2008-09-03 2011-10-26 三菱樹脂株式会社 セパレータ用積層多孔性フィルム、およびその製造方法
CN102171855A (zh) * 2008-09-03 2011-08-31 三菱树脂株式会社 隔板用叠层多孔膜
CN101752539A (zh) 2008-12-01 2010-06-23 比亚迪股份有限公司 一种锂离子二次电池用聚酰亚胺隔膜以及锂离子电池
US11139534B2 (en) * 2011-12-09 2021-10-05 Tokyo Metropolitan University Lithium secondary battery separator and method of manufacturing same
JP6226879B2 (ja) * 2012-11-27 2017-11-08 日本ゴア株式会社 二次電池およびそれに用いるセパレータ
US8999553B2 (en) * 2013-03-15 2015-04-07 Ford Global Technologies, Llc Rechargeable battery with shutdown layer comprising a low melting point material and an electrically conductive material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
REHWINKEL C ET AL: "Surface activation of perfluorinated polymers", JOURNAL OF FLUORINE CHEMISTRY, ELSEVIER, NL, vol. 104, no. 1, 1 June 2000 (2000-06-01), pages 19 - 28, XP004199229, ISSN: 0022-1139, DOI: 10.1016/S0022-1139(00)00223-2 *

Also Published As

Publication number Publication date
EP3151328A4 (en) 2017-11-15
JPWO2015182615A1 (ja) 2017-04-20
US20170155116A1 (en) 2017-06-01
KR101950083B1 (ko) 2019-02-19
CA2950400C (en) 2019-03-12
EP3151328A1 (en) 2017-04-05
JP6297145B2 (ja) 2018-03-20
US10181593B2 (en) 2019-01-15
CA2950400A1 (en) 2015-12-03
CN106415913A (zh) 2017-02-15
WO2015182615A1 (ja) 2015-12-03
CN106415913B (zh) 2020-03-06
KR20170016881A (ko) 2017-02-14

Similar Documents

Publication Publication Date Title
EP3422444B1 (en) Anode for lithium secondary battery comprising mesh-shaped insulating layer, and lithium secondary battery comprising same
EP3151328B1 (en) Rechargeable battery and separator used therein
EP3429014B1 (en) Lithium secondary battery having lithium metal formed on cathode and manufacturing method therefor
US9166250B2 (en) Separator for battery, method for manufacturing the same, and lithium secondary battery
JP4832430B2 (ja) リチウムイオン二次電池用セパレータ及びリチウムイオン二次電池
EP0803925A1 (en) Nonaqueous polymer cell and method of producing polymer for nonaqueous polymer cell
JP2001135359A (ja) 非水電解質電池
KR102250172B1 (ko) 리튬 이온 이차 전지용 분리막 및 이를 포함하는 리튬 금속 전지
JP4606705B2 (ja) 非水系二次電池用セパレータ及び非水系二次電池
EP2930766B1 (en) Secondary battery and separator used therein
EP1176660A2 (en) Non-Aqueous electrolyte secondary battery
US8877380B2 (en) Positive active material, method of preparing the same, and lithium battery including the positive active material
CN112585796B (zh) 固体电解质膜、其制造方法以及包含其的固态电池
JP2004253380A (ja) リチウムイオン二次電池用セパレータ及びリチウムイオン二次電池
JP3931413B2 (ja) リチウム二次電池用正極の製造方法
JP2010010093A (ja) 二次電池用電極群の製造方法および二次電池の製造方法
JPH09259923A (ja) ポリマー電池及びその製造法
JP4240008B2 (ja) 多孔性リチウムイオン導電性ポリマー電解質の製造方法。
JP5924079B2 (ja) リチウムイオン２次電池用セパレータ、及びそれを用いたリチウムイオン２次電池

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20161213

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20171017

RIC1 Information provided on ipc code assigned before grant

Ipc: H01M 10/052 20100101ALI20171009BHEP

Ipc: H01M 10/42 20060101ALI20171009BHEP

Ipc: H01M 10/058 20100101AFI20171009BHEP

Ipc: H01M 4/38 20060101ALI20171009BHEP

Ipc: H01M 2/16 20060101ALI20171009BHEP

Ipc: H01M 10/054 20100101ALI20171009BHEP

Ipc: H01M 2/34 20060101ALI20171009BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20190130

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: W.L. GORE & ASSOCIATES G.K.

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602015077739

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: H01M0010058000

Ipc: H01M0050414000

RIC1 Information provided on ipc code assigned before grant

Ipc: H01M 50/572 20210101ALI20210922BHEP

Ipc: H01M 50/449 20210101ALI20210922BHEP

Ipc: H01M 50/446 20210101ALI20210922BHEP

Ipc: H01M 10/42 20060101ALI20210922BHEP

Ipc: H01M 4/38 20060101ALI20210922BHEP

Ipc: H01M 10/058 20100101ALI20210922BHEP

Ipc: H01M 10/052 20100101ALI20210922BHEP

Ipc: H01M 10/054 20100101ALI20210922BHEP

Ipc: H01M 50/451 20210101ALI20210922BHEP

Ipc: H01M 50/426 20210101ALI20210922BHEP

Ipc: H01M 50/414 20210101AFI20210922BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20211119

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602015077739

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1478080

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220415

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20220323

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220623

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220623

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1478080

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220323

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220624

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220725

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220723

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602015077739

Country of ref document: DE

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20220531

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220526

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220531

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220531

26N No opposition filed

Effective date: 20230102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220526

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220531

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230511

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20230419

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20150526

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20240418

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20240418

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220323